Hydroconversion process and catalyst used therein

Abstract

 The present invention relates to a hydroconversion process which comprises reacting a hydrocarbon feed rich in normal and/or slightly branched paraffins with a source of hydrogen in the presence of a catalyst composition which comprises two different metals from group VIII of the periodic table of elements, the first metal being preferably selected from platinum, palladium or iridium, and the second metal being preferably selected from nickel, cobalt or iron, on a support which comprises at least two different crystalline molecular sieves having each pores with a largest diameter in a range of 0.56-0.74 nm, one of the molecular sieves being preferably ultrastable Y zeolite (USY), and a binder of up to 25 weight percent, based on the total weight of the support, at a pressure of about 1-5 bar and at a temperature in the range of 200-300°C, with a hydrogen/feed molar ratio in the range of from 5 to 15 mol/mol; as well as a catalyst composition used therein.

Description

[0001] The present invention relates to a hydroconversion process as well as to a catalyst composition which may be utilized in that process. The hydroconversion process of the present invention comprises the sequential steps of isomerization followed by cracking of multi-branched intermediate isomers. Thus, the hydroconversion process combines isomerization and cracking steps.

[0002] The demand for different fuels has almost doubled in the past thirty years due to the car industry and new engine developments. During the coming decades petroleum will still be the main source of energy fuels and will supply a large share of the fuel required by industry and virtually all the fuel required for transport. Concern over the negative effects of fuel and oil usage on the environment has caused severe changes in regulations with impact on gasoline, other jet fuels and lubricating oils. In particular, the forthcoming gasoline regulations are becoming more and more complex increasing the requirements for high quality of fuels. To meet these challenges, the progressive improvements and in some cases technological breakthroughs are required.

[0003] So far, methyl tertiary butyl ether (MTBE) has played a key role in the development of the today's regulatory approach to control vehicle emissions. However, the discovery of MTBE contamination of surface and ground water has prompted review of the environmental drawbacks associated with the use of MTBE as gasoline blend component. Additionally, new regulations for aromatic compounds, olefins, sulfur and nitrogen have been discussed.

[0004] At the present time, refiners are looking for more environmentally safe octane blending components as MTBE alternatives.

[0005] Petroleum fractions contain significant amounts of n-alkanes. The isomerization of alkanes into branched isomers is one of the important processes in the petroleum refining. The highly branched paraffins with 5-10 carbon atoms would be best to fulfill the recent requirements of the reformulated gasoline. Therefore, the production of paraffin based high-octane gasoline blendstock such as isomerates from hydroconversion of n-paraffins might be a key technology for gasoline supply to cope with future gasoline regulations.

[0006] There have been significant advantages over the last two decades on the selective hydroisomerization of light naphtha (C₅-C₆) into their branched isomers to be used as motor fuel components. Recently, the hydroisomerization of light naphtha to branched isomers was introduced in petroleum industry. Isomerization of light naphtha streams gives high octane number branched C₅-C₆-isomers which are good gasoline components; and isobutane, an important raw product for alkylation. This process typically produces an increase of 10-18 octane numbers.

[0007] To fulfill the future needs for gasoline with high octane number enhanced by environmentally friendly way, it is necessary to improve the hydroconversion processes of high n-paraffins. The combined selective isomerization and hydrocracking of mid-cut naphtha fractions and high n-paraffins is among the most promising ways to realize the above mentioned needs.

[0008] The challenge for the research in that area is to find an effective catalyst favoring the sequential isomerization with following selective hydrocracking of high n-paraffins into LPG (liquefied petroleum gas) which is suitable for automobile applications, and high octane gasoline pool components.

[0009] There are a few proposals of processes for the combined isomerization and cracking of the normal and/or or slightly branched C₉+ range paraffins into high octane gasoline pool components in the art.

[0010] For example, US 3,969,277 provides a process for the preparation of a tungsten supported on erionite catalyst. The process comprises contacting feedstock with the catalyst in the presence of hydrogen at high temperatures and pressures. The process realizes at 400°C a yield of up to 86.3 weight percent gasoline with octane number 97 and 13.7 weight percent of a mixture of gases C₁-C₄.

[0011] EP 1 640 434 A1 provides a one-stage combined isomerization and cracking of a naphtha boiling range hydrocarbonaceous feedstock with a source of hydrogen in the presence of catalyst composition which comprises a Group VIII metal and optionally a Group VIb metal on a support. The support comprises at least 20 weight percent of a crystalline molecular sieve having pores in the range of from 0.65 nm to 0.9 nm, and a pressure in the range of 10 to 120 atm, a temperature in the range of from 300 to 450°C. It is related to the sequential isomerization and cracking for the production of LPG with a selectivity of up to 80 weight percent, with a C₃-C₄ ratio of 0.6 while keeping C₁-C₂ yield at about 10 weight percent of the feed. The process produces only 10 weight percent of the lighter residual naphtha with an octane number of greater than 87, having a higher concentration of retained aromatics.

[0012] It is an object of the present invention to provide a process for hydroconversion of a hydrocarbon feed rich in normal and/or slightly branched paraffins which overcomes the drawbacks of the prior art. Especially, the process shall result in products having low olefin and low aromatic content, as well as a low content of C₁-C₃ gaseous hydrocarbons. The product shall be also substantially without sulfur and nitrogen. Preferably, the product shall be LPG with high concentration of isobutane and high octane gasoline pool components, wherein the products can be easily utilized in automobile applications.

[0013] Additionally, it is an object of the present invention to provide a catalyst composition which is suitably used in that process.

[0014] The first object is achieved by a hydroconversion process which comprises reacting a hydrocarbon feed rich in normal and/or slightly branched paraffins with a source of hydrogen in the presence of a catalyst composition which comprises two different metals from group VIII of the periodic table of elements, the first metal being preferably selected from platinum, palladium or iridium, and the second metal being preferably selected from nickel, cobalt or iron, on a support which comprises at least two different crystalline molecular sieves having each pores with a largest diameter in a range of 0.56-0.74 nm, one of the molecular sieves being preferably ultrastable Y zeolite (USY) and a binder of up to 25 weight percent, based on the total weight of the support, at a pressure of about 1-5 bar and at a temperature in the range of 200-300°C, with a hydrogen/feed molar ratio in the range of from 5 to 15 mol/mol. Preferably, the hydrocarbon feed comprises C₉+ normal paraffins and/or mid-cut naphtha petroleum fraction, preferably hydrotreated naphtha.

[0015] Preferably, the two different metals of the catalyst composition are Pt-Ni, Pd-Ni, Pt-Fe, Pt-Ir or Pt, Co, preferably Pt-Ni.

[0016] In one embodiment the at least two different crystalline molecular sieves are selected from USY, ZSM-5 and zeolite beta.

[0017] The process may be carried out in tubular a bed type reactor having a space velocity in the range of 0.5 to 4.0 h^-1.

[0018] It is also preferred, that the binder comprises gamma-Al₂O₃, SiO₂, ZrO₂, TiO₂ or any mixtures thereof.

[0019] The crystalline molecular sieves are preferably in acid form.

[0020] The second object is achieved by a catalyst composition for hydroconversion of a hydrocarbon feed rich in normal and/or slightly branched paraffins, comprising two different metals from group VIII of the periodic table of elements, the first metal being preferably selected from platinum, palladium or iridium, and the second metal being preferably selected from nickel, cobalt or iron, on a support which comprises at least two different crystalline molecular sieves having each pores with a largest diameter in a range of 0.56-0.74 nm, one of the molecular sieves being preferably ultrastable Y zeolithe (USY), and a binder of up to 25 weight percent, based on the total weight of the support.

[0021] Surprisingly it was found that the inventive process results in products in high amounts and selectivities which can be either successfully used in alkylation (isobutane) or are very suitable for automobile applications. The products of the inventive process have low contents of olefins, aromatics and C₁-C₃ gaseous hydrocarbons. Additionally, the products are substantially free of sulfur and nitrogen. The hydroconversion process can be carried out in one stage combining isomerization and cracking. Further, the process can produce up to 95-96 weight percent of LPG (with high concentration of isobutane and being suitable for automobile application) and gasoline pool components with a research octane number (RON) >90 and complete conversion of the feed. The products of the process contain less than 5.0 weight percent of propane and only traces of C₁-C₂ hydrocarbons. The C₄ fraction of the produced products contains more than 90 weight percent of isobutane, which is an ideal feedstock for alkylation.

[0022] Most preferably, the present invention provides a hydroconversion process involving sequential isomerization with following cracking steps of the feed with a source of hydrogen for production of LPG and gasoline pool components having octane number of >90 using especially Ni-Pt or Ni-Pd on USY-ZSMS/(γ-Al₂O₃+ZrO₂+TiO₂) composite catalyst at a temperature in a range of 220-280°C under normal pressure and at a space velocity in the range of 0.5 to 4.0 h^-1 in a tubular bed type reactor wherein the hydrogen to feed ratio is in a range of from 5 to 15 mol/mol. The present invention enables high levels of conversion to be employed, so that yields of octane blending components are produced directly from the feed in a single pass. In addition, yields of low end cracking products, such as methane, ethane and propane, are minimized in the inventive process.

[0023] It was found, that for example, the yield of iC₅ in a hydrocracking product obtained from n-C₁₀ feed can be increased significantly by combination of different zeolites and modification with different metals.

Detailed description of the invention

Feed

[0024] The feed used in the process of the present invention is rich in normal and/or slightly branched paraffins. The feed of the inventive process preferably comprises mid-cut naphtha petroleum fraction and/or C₉⁺ normal paraffins or mixtures thereof. Alternatively or additionally it may also comprise a feed rich in normal and/or slightly branched light and/or mid-cut naphtha range petroleum fractions. Feedstock comprising C₁₀-C₂₀-paraffins from Fisher-Tropsch-synthesis may also be treated by the present process. Preferably, the process operates with hydrotreated feeds. A preliminary hydrotreating step may be carried out using a conventional hydrotreating catalyst to remove sulfur and nitrogen.

Hydroconversion (combining hydrocracking and isomerization)

[0025] The feedstock is subjected to a hydroconversion process in the presence of hydrogen involving sequential isomerization and selective cracking in a single pass to produce LPG (with high concentration of isobutane and suitable for the automobile applications) and high octane gasoline branched isoparaffins.

[0026] Within a wide range of zeolite-based catalysts for hydroconversion, it has now been found that a combination of certain zeolites with different pore morphology, modified with different metals, can be designed for the composite systems, which in the presence of hydrogen selectively convert the feedstock with long carbon chains to octane blending isoparaffins, while minimizing formation of C₁-C₃ gaseous hydrocarbons. Molecular sieves of interest in the present invention are crystalline materials having defined pores or channels within a regular crystalline structure. The structures and their pore or channel sizes are well documented in the art, for example in the "Atlas of Zeolite Framework Types", Ch. Baerlocher, W.M. Meier, and D.H. Olson, 5th Edition, Elsevier Amsterdam 2001, which also documents references describing how these materials are to be prepared. As used herein "pores with a largest diameter" are crystallographic free diameters calculated as in the "Atlas of Zeolite Framework Types", idem. The term denotes the largest channel width or pore diameter in the molecular sieve structure.

[0027] In the context of the present specification, the term "molecular sieve" also includes the corresponding (hydrothermally) stabilized and dealuminated derivatives and such derivatives as may be obtained by isomorphous substitution and cation exchange. Methods for cation exchange, (hydrothermal) stabilization, dealumination and isomorphous substitution of molecular sieves are well known in the art and are not therefore further discussed in the present specification. The term "crystalline molecular sieve" will also be used herein interchangeably with the term "zeolite". Most preferably, the molecular sieves used in the present invention are in its acid form.

[0028] It was further surprisingly found that a composition comprising zeolite USY (or USY+Zeolite Beta) in combination with ZSM-5 shows synergistic properties. Zeolite Y exhibits the faujasit structure. It has a three dimensional pore structure with pores running perpendicular to each other in the x, y and z planes, and the pore diameter is 0.74 defined by a 12-membered oxygen ring, and leads into a larger cavity of diameter of 1.2 nm. Hydrothermal dealumination of Y zeolite results in the expulsion of tetrahedral aluminum from the framework into non-framework positions increasing the framework silica-to-alumina ratio, which leads to the formation of ultra-stable Y zeolites (USY).

[0029] Zeolite ZSM-5 has two types of pores having diameter of 0.53-0.56 nm, both formed by 10-membered oxygen rings.

[0030] Zeolite beta consists of an intergrowth of two distinct structures. These structures grow as two dimensional channels and they randomly alternate between the two. Tetragonal crystal structure with straight 12-membered ring channels with crossed 10-membered ring channels.

[0031] The catalyst composition of the present invention contains binder materials. Many inorganic oxides such as alumina, silica, zirconia, titanium oxide or their mixtures can be used as a binder. Most preferred as a binder is a mixture of above mentioned oxides. Most preferred supports contain from 35 to 70 weight percent of zeolite USY, 15 to 20 weight percent of ZSM-5 with the balance being the binder.

[0032] As first metal components of the catalyst are preferably used platinum, palladium or iridium (more preferred platinum), which are utilized in combination with the second metal component selected from nickel, cobalt or iron (more preferably nickel). According to the present invention, the catalyst may contain a noble metal in the range of from 1.3 to 2.8 weight percent, preferably 1.3 to 2.0 weight percent.

[0033] Suitable metal combination procedures include impregnation, wherein the support is contacted with the solution of a suitable salt of the metal component. Suitably the metal salt solutions can be aqueous or organic solutions of soluble salts of metals, preferred organic solutions (cyclohexane, benzene, etc.). Examples of soluble salts in hydrocarbons are acetyl acetonates of the used metals. Following the incorporation of metals onto the support, the catalyst composition is dried at a temperature of from 100 to 200°C for a period of 1 to 3 hours, and then calcined at a temperature in the range of from 350 to 450°C.

[0034] In a more preferred embodiment, the process of the present invention is carried out using a wide variety of C₉+ normal paraffins range feedstock with a source of hydrogen in a single pass in the presence of Ni-Pt on USY/ZSM-5/(γ-Al₂O₃+ZrO₂+TiO₂) catalyst at normal or low (2-5 bar) pressure, at a temperature at a range of 230-300°C and in a reactor wherein the hydrogen to feed ratio is the range of 7-12 mol/mol.

[0035] In the process of the invention, the catalyst used has been found to exhibit a very high stability as will be demonstrated below.

[0036] Preferably, the tubular fixed bed reactor is down flow reactor.

[0037] Additional advantages and features of the present invention can be taken from the further more detailed description of examples, taken together with the drawings wherein

Fig. 1 illustrates a typical laboratory flow sheet diagram for the process of the invention; and

Fig. 2 is a graph showing catalyst stability on stream in hydroconversion using hexadecane as feedstock in the process of the present invention.

[0038] The present invention will now be illustrated by the following examples.

Examples

Example 1. Catalyst preparation

[0039] A number of catalysts were prepared utilizing different zeolite containing supports. The following procedure is exemplary of how each support was prepared.

Preparation of catalyst 1:

[0040] 6.0 grams of zeolite USY (grade CBV 417 Zeolyst) and 2.0 grams of ZSM-5 (Zeolyst) were mixed with a mixture of 2.0 (Al(OH)₃+ZrO₂+TiO₂) and allowed to extensive stirring for 30 minutes. Then the resulting mixture was dried for 3-4 hours 110-120°C in a static furnace. After that the solid mass was calcined in a well vented static furnace for 3 hours at 450-500°C.

[0041] Then 5 grams of the received support were placed in the rotating vessel and 100 ml of n-cyclohexane solution containing 0.05 weight percent platinum (in the form H₂PtCl₆) and 0.025 weight percent nickel (in the form of Ni(C₂H₇O₅)₂) was added. Mixing was carried out at room temperature for 1 hour, followed by slow evaporation of the solvent in a rotary evaporator. The material was then heated for 2-3 h at 110-120°C and treated under hydrogen flow (60-80 ml/min) at 500°C for 3 hours.

[0042] Following the same procedure as illustrated above, the catalyst composition as listed in table 1 below were prepared:

Table 1: List of prepared catalyst compositions

Catalyst	Composition of Support (wt%) Zeolite	Binder	Supported metals (wt%)
1	60%USY/ZSM-5(15%)	25%[γ-Al2O3(10)+ZrO2(8)+	1.3%
		TiO2(7)]	[Pt(1)+Ni(0.3)]
2	65%USY/ZSM-5(15%)	20%[γ-Al2O3(10)+ZrO2(5)+	1.5%
		TiO2(5)]	[Pt(1)+Pd(0.5)]
3	70%USY/ZSM-5(15%)	15% γ-Al2O3	2.5%
			[Pt(1.5)+Ni(1)]
4	60%USY/ZSM-5(20%)	25%[γ-Al2O3(10)+ZrO2(5)+	2.8%
		TiO2(5)]	[Pt(1.3)+Fe(0.5)]
5	35%USY/ZSM-5(20)/Beta(25)	20%[γ-Al2O3(10)+ZrO2(5)+	2%
		TiO2(5)]	[Pt(1.5)+Ni(0.5)]
6	60% USY/ZSM-5(20%)	20%[γ-Al2O3(15)+ZrO2(5)]	2.0% [Pt(1)+Pd(1)]
7	60% USY/ZSM-5(20%)	20%[γ-Al2O3(15)+TiO2(5)]	2.2%
			[Pd(1.5)+Ni(0.7)]
8	60% USY/ZSM-5(20%)	20%[γ-Al2O3(15)+TiO2(5)]	2.3%
			[Pt(0.8)+Pd(1.5)]
9	60% USY/ZSM-5(15%)	20%[γ-Al2O3(15)+ZrO2(5)+	1.5%
		TiO2(5)]	[Pt(1)+Co(0.5)]
10	60% USY/ZSM-5(20%)	20%[γ-Al2O3(10)+ZrO2(5)+	1.5%
		TiO2(5)]	[Pt(1)+Ir(0.5)]

Example 2. Catalyst activity testing

[0043] The activity and selectivity testing of the catalyst compositions prepared was conducted at atmospheric pressure in a laboratory pilot-unit with a tubular flow fixed-bed reactor connected to a gas chromatograph Varian-RGA Model 3600 GC.

[0044] Figure 1 illustrates a typical laboratory flow sheet diagram for the process of the invention. Nitrogen and hydrogen gas are introduced via a flow controller, a check wave, a needle valve and a three way valve and a heater into the reactor. Also introduced into the reactor is a feed which is introduced via a feed pump and the heater. Products from the reactor are transferred to a condenser and are then analyzed by gas chromatograph.

[0045] The testing was carried out using the following conditions:

PP 1 bar

[0046] Individual normal paraffins C₉-C₁₆ (purity > 99%) and a mid-cut naphtha fraction from Yanbu Refinery (Saudi Arabia) with the following initial properties were used for the catalyst activity and selectivity testing.

Table 2. Properties of hydrotreated mid-cut naphtha fraction used as a feed

Property	Mid-cut Naphtha
Density, 15°C	0.7391
Paraffins, % vol	35.219
Iso-Paraffins, % vol	35.172
Olefins, % vol	0.461
Naphthenes, % vol	15.032
Aromatics, % vol	13.582

Distillation, °C
IBP	92.10
10%	108.2
30%	116.6
50%	125.7
70%	137.6
90%	152.8
FBP	180.10
RON (calculated)	53.39

IBP = initial boiling point; FBP = final boiling point

[0047] The experimental conditions as mentioned above were used for a typical run to test the catalytic performance as follows:

0.3-0.5 g of crushed and sieved (30-60 mesh) catalyst sample was loaded into a stainless steel reactor tube. A thermocouple was placed on the center of the catalyst bed to monitor the reaction temperature. The catalyst was calcined at 500°C for 3 hours in an nitrogen atmosphere, and was then reduced with hydrogen at 250°C for 2 hours.

[0048] After preparing the catalyst, feed was dosed via mass flow controllers and mixed with a stream of hydrogen gas at normal pressure. The combined feed stream was first heated to the reaction temperature and was then fed to the down-flow fixed bed reactor where hydroconversion reaction took place. Reactor temperatures in the range of 230-300°C were scanned to achieve high conversion levels. All the reaction products were analyzed online by a gas chromatograph on a 30 m long DB1 capillary column. Each percentage of reaction products was calculated from the chromatographs as a mass of that product divided by the mass of hydrocarbon reacted. For the calculation of octane performance, the reactor effluent containing the reaction products was fed to the condenser where the gas was separated from the liquid products and analyzed on a PIONA chromatograph.

[0049] The results of the testing of individual C₉+ normal paraffins and mid-cut naphtha petroleum fractions are shown in tables 3 to 13.

Table 3: Products distribution of n-Nonane hydroconversion on catalyst [1] at 300°C (wt%)

	Parafins	Iso-Paraffins	Olefins	Naphthenes	Aromatics	Total
C1	0.098	0	0	0	0	0.098
C2	0.108	0	0	0	0	0.108
C3	5.351	0	0	0	0	5.351
C4	8.553	19.762	0	0	0	28.315
C5	7.605	25.225	0	0	0	32.830
C6	0.813	8.676	0	0.332	0.004	9.824
C7	0.197	0.551	0.001	0.273	0	1.021
C8	0.166	6.439	0.224	3.602	0.856	11.287
C9	0.080	8.320	0.237	2.290	0	10.927
Total:	22.971	68.973	0.462	6.496	0.860	99.761
Oxygenates: 0		Total C10+: 0	Unknowns: 0.239		Grand Total: 100.0

OCTANE NUMBER (calculated): 95.89

Table 4: Products distribution of n-Nonane hydroconversion on catalyst [3] at 260°C (wt%)

	Parafins	Iso-Paraffins	Olefins	Naphthenes	Aromatics	Total
C1	0.065	0	0	0	0	0.065
C2	0.024	0	0	0	0	0.024
C3	2.826	0	0	0	0	2.826
C4	8.258	30.401	0	0	0	38.660
C5	12.456	36.062	0	0	0	48.518
C6	1.024	4.303	0	0.174	0.003	5.504
C7	0.087	0.546	0.001	0.114	0	0.747
C8	0.030	0.179	0.017	0.343	0.017	0.587
C9	0.020	1.572	0.166	0.102	0.324	2.184
C10	0.084	0.022	0	0.781	0	0.886
Total:	22.971	68.973	0.462	6.496	0.860	99.761
Oxygenates: 0		Total C 10+: 0	Unknowns: 0		Grand Total: 100.0

OCTANE NUMBER (calculated): 99.94

Table 5: Products distribution of n-Nonane hydroconversion on catalyst [2] at 300°C (wt%)

	Parafins	Iso-Paraffins	Olefins	Naphthenes	Aromatics	Total
C1	0.111	0	0	0	0	0.111
C2	0.049	0	0	0	0	0.049
C3	4.920	0	0	0	0	4.920
C4	9.373	25.292	0	0	0	34.666
C5	9.472	33.084	0	0	0	42.557
C6	1.002	7.901	0	0.080	0	8.983
C7	0	0	0	0	0	0
C8	0	0	0	0	0	0
C9	1.519	3.629	0.311	3.256	0	8.71
Total:	21.477	69.907	5.279	3.337	0	100
Oxygenates: 0		Total C9+: 0	Unknowns: 0	Grand Total: 100.0

OCTANE NUMBER (calculated): 95.34

Table 6: Products distribution of n-Decane hydroconversion on catalyst [1] at 280°C (wt%)

	Parafins	Iso-Paraffins	Olefins	Naphthenes	Aromatics	Total
C1	0.045	0	0	0	0	0.045
C2	0.062	0	0	0	0	0.062
C3	3.445	0	0	0	0	3.445
C4	4.714	16.495	0	0	0	21.209
C5	5.670	23.706	0	0	0	29.376
C6	4.758	24.905	0	0.531	0.004	30.194
C7	0.419	5.675	0.001	0.364	0	6.458
C8	0.114	0.812	0.038	0.182	0.061	1.208
C9	0.56	0.086	0.200	0.046	1.047	1.435
C10	0.686	2.297	0.347	0.486	1.056	4.871
C11	0	1.234	0	0	0	1.234
Total:	19.969	75.209	4.029	1.609	2.164	99.535
Oxygenates: 0		Total C11+: 0	Unknowns: 0.465		Grand Total: 100.0

OCTANE NUMBER (calculated): 90.01

Table 7: Products distribution of n-Decane hydroconversion on catalyst [3] at 240°C (wt%)

	Parafins	Iso-Paraffins	Olefins	Naphthenes	Aromatics	Total
C1	0.040	0	0	0	0	0.040
C2	0.017	0	0	0	0	0.017
C3	1.536	0	0	0	0	1.536
C4	2.486	16.596	0	0	0	19.082
C5	5.396	27.877	0	0	0	33.273
C6	5.682	21.263	0	0.108	0	27.053
C7	0	0.222	0	0.098	0	0.320
C8	0	0.190	0	0.099	0.282	0.572
C9	0.018	0.876	1.180	1.081	0	3.155
C10	0	6.677	0.002	0.067	0	6.745
Total:	15.177	73.701	1.182	1.452	0.282	91.795
Oxygenates: 0		Total C 10+: 0	Unknowns: 8.205		Grand Total: 100.0

OCTANE NUMBER (calculated): 91.45

Table 8: Products distribution of n-Decane hydroconversion on catalyst [5] at 270°C (wt%)

	Parafins	Iso-Paraffins	Olefins	Naphthenes	Aromatics	Total
C1	0.014	0	0	0	0	0.014
C2	0.011	0	0	0	0	0.011
C3	3.321	0	0	0	0	3.321
C4	4.650	15.743	0	0	0	20.393
C5	5.709	21.695	0	0.738	0	28.142
C6	4.746	25.136	0	0.283	0	30.165
C7	0	6.004	0	0.007	0	6.011
C8	0.077	0.150	0	0.062	0	0.289
C9	0	0	0.027	0.093	0.952	1.073
C10	0	5.902	0.406	0.533	0	6.841
Total:	18.528	74.629	0.433	1.717	0.952	96.259
Oxygenates: 0		Total C11+: 0	Unknowns: 3.741		Grand Total: 100.0

OCTANE NUMBER (calculated): 90.31

Table 9: Hydroconversion of C₁₁-C₁₆ n-Alkanes on catalyst [4]

Hydrocarbon	n-C11	n-C12	n-C14	n-C15	n-C16
Temperature (K)	503	503	493	493	483
Conversion (%)	100	100	100	100	100

Products Distribution (wt.%)
C1+C2	-	-	-	-	-
C3	2.5	2.0	0.8	0.6	0.9
ΣC4 (iso/normal)	18.1 (3.7)	15.2(5.9)	5.9(4.9)	4.8(4.2)	8.2(4.9)
ΣC5 (iso/normal)	23.7 (4.8)	19.8 (7.1)	8.5 (7.4)	6.9 (5.5)	12.7 (6.9)
ΣC6 (iso/normal)	27.2 (5.2)	21.3(8.1)	10.3 (6.9)	8.7 (5.9)	15.3 (9.5)
ΣC7 (iso/normal)	25.6 (7.4)	23.5 (10.8)	14.1 (9.7)	13.1 (7.2)	18.3 (13.1)
ΣC8 (iso/normal)	2.9 (21.5)	18.2(9.1)	18.6 (9.9)	18.0(8.1)	17.8(15.0)
ΣC9 (iso/normal)	-	-	29.2 (9.6)	27.7 (10.2)	19.6 (14.4)
ΣC10 (iso/normal)	-	-	12.6 (10.6)	20.2 (11.4)	7.2 (100% iso)
ΣC4+(iso/normal)	97.5(8.5)	98.0(8.2)	99.2(8.4)	99.4(7.5)	99.1(10.1)

Table 11: Products distribution of Mid-cut hydroconversion on catalyst [5] at 300°C (wt%)

	Parafins	Iso-Paraffins	Olefins	Naphthenes	Aromatics	Total
C1	0.035	0	0	0	0	0.035
C2	0.081	0	0	0	0	0.081
C3	1.476	0	0	0	0	1.476
C4	1.566	4.323	0	0	0	5.889
C5	1.493	5.443	0	0	0	6.935
C6	1.089	4.014	0	1.262	0.061	6.425
C7	2.613	11.891	0	7.719	0	22.223
C8	0.446	20.760	0.994	16.442	4.228	42.870
C9	1.039	5.599	0.041	0.915	1.002	0.685
C10	0.108	0.171	0	2.110	0.163	2.553
C11	0	0.011	0	0	0.096	0.106
C12	0.021	0.049	0.011	0	0.299	0.380
C13	0.424	0	0.022	0	0	0.446
Total:	10.033	52.262	1.068	28.448	5.848	99.554
Oxygenates: 0		Total C14+: 0	Unknowns: 0.446		Grand Total: 100.0

OCTANE NUMBER (calculated): 89.97

Table 12: Products distribution of Mid-cut hydroconversion on catalyst [8] at 280°C (wt%)

	Parafins	Iso-Paraffins	Olefines	Naphthenes	Aromatics	Total
C1	0.011	0	0	0	0	0.011
C2	0.065	0	0	0	0	0.065
C3	4.157	0	0	0	0	4.157
C4	3.923	14.195	0	0	0	18.118
C5	1.752	13.690	0	0	0	15.443
C6	2.201	8.129	0	0.715	0	11.044
C7	3.017	19.802	1.549	8.173	0	32.542
C8	0	7.100	1.007	5.600	0.030	13.737
C9	0	0.689	0.259	0.639	0	1.587
C10	0	0.049	0	0.018	0	0.067
C11	0	0.064	0	0	0	0.064
Total:	15.126	63.718	2.815	15.145	0.030	96.834
Oxygenates: 0		Total C11+: 0	Unknowns: 3.166		Grand Total: 100.0

OCTANE NUMBER (calculated): 91.89

Table 13: Products distribution of Mid-cut hydroconversion on catalyst [3] at 300°C (wt%)

	Paraffins	Iso-Paraffins	Olefins	Naphthenes	Aromatics	Total
C1	0.146	0	0	0	0	0.146
C2	0.090	0	0	0	0	0.090
C3	7.546	0	0	0	0	7.546
C4	7.813	17.924	0	0	0	25.738
C5	4.117	14.866	0	0	0	18.983
C6	2.600	8.159	0	1.704	1.199	13.662
C7	1.871	11.154	0	0.695	0	13.721
C8	0.750	10.064	0.828	0.809	2.286	14.737
C9	0.114	1.588	0.331	0.121	0.008	2.162
C10	0	0.299	0.408	0.009	0.017	0.733
C11	0	0.154	0	0	0	0.154
Total:	25.047	64.209	1.567	3.338	3.510	97.672
Oxygenates: 0		Total C11+: 0	Unknowns: 2.328		Grand Total: 100.0

OCTANE NUMBER (calculated): 91.78

[0050] From Tables 3-6, it can be taken that catalysts used in the process of the present invention for the hydroconversion yield high amounts of C₄-C₅ (77-87 wt%) from n-nonane at a temperature interval of 260-300°C and normal pressure. The yield of C₄+ hydrocarbons of products produced achieved 94-95 wt% containing about 70 wt% of branched isomers of paraffins, 3.3-6.5 wt% of naphtha fraction and very low concentrations of olefins and aromatics. Only traces of methane and ethane, and 2.5-4.9 wt% of propane was observed among produced products. Calculated octane numbers of C₄+ products by PIONA method achieved 95-100. From Tables 6-8, it can be taken that the main products of n-decane hydroconversion over catalysts used in the process of the present invention were isomers of C₄-C₆-hydrocarbons (77.7-80.3 wt%). The yield of C₄+ hydrocarbons of produced products achieved 96-98 wt% containing about 75 wt% of branched isomers of paraffins, 2-3 wt% of naphtha fraction and very low concentrations of olefins and aromatics. Only traces of methane and ethane, and 3.3-3.5 wt% of propane was observed among the products. The calculated octane numbers of produced C₄+ products by PIONA method achieved 90.1-90.3.

[0051] As can be taken from Table 9, by increasing the molecular weight of the feedstock resulted in a complete conversion of n-paraffins to increase of C₄+ fraction of more than 99%. The amount of gasoline range isoparaffins C₅-C₁₀ also increases significantly. The yield of C₅+ hydrocarbons increases from 79.4 to 91.1 wt%, when n-paraffin chain increases from C₁₁ to C₁₆. The isomer/normal paraffin ratio of the process products also increases considerably. It is remarkable that the yield of propane decreases from 2.5 for n-C₁₁ to 0.8-0.9 for C₁₄-C₁₆ normal paraffins, and no methane and ethane products are formed.

[0052] From Tables 10-12 it can be seen that the catalysts used in the process of the present invention convert a mid-cut naphtha fraction to gasoline components with octane number 90.1-91.9. The reaction products contain more than 92-98 wt% of C₄+ hydrocarbons depending on the catalyst composition used, consisting mostly of isoparaffins (up to 64.2 wt%) and naphthenic hydrocarbons (up to 28.4 wt%). No methane and ethane are formed.

[0053] Finally, the stability of the inventive catalyst composition was tested, normal hexadecane in the presence of hydrogen was fed to a tubular reactor containing a catalyst bed of Ni-Pt/USY/ZSM-5/(Al₂O₃+ZrO₂+TiO₂) at 220°C and at normal pressure during one month of continuous operation. During this period the catalyst had very high stability with a very low deactivation rate, see Figure 2.

[0054] The features disclosed in the foregoing description, the claims and the drawings may, both separately and in any combination thereof, be material for realizing the invention in divers forms thereof.

Claims

1. Hydroconversion process which comprises reacting a hydrocarbon feed rich in normal and/or slightly branched paraffins with a source of hydrogen in the presence of a catalyst composition which comprises two different metals from group VIII of the periodic table of elements, the first metal being preferably selected from platinum, palladium or iridium, and the second metal being preferably selected from nickel, cobalt or iron, on a support which comprises at least two different crystalline molecular sieves having each pores with a largest diameter in a range of 0.56-0.74 nm, one of the molecular sieves being preferably ultrastable Y zeolite (USY), and a binder of up to 25 weight percent, based on the total weight of the support, at a pressure of about 1-5 bar and at a temperature in the range of 200-300°C, with a hydrogen/feed molar ratio in the range of from 5 to 15 mol/mol.

2. Hydrocracking and isomerization process according to claim 1, wherein the hydrocarbon feed comprises C₉+ normal paraffins and/or mid-cut naphtha petroleum fraction, preferably hydrotreated naphtha.

3. Process according to claim 1 or 2, wherein the two different metals of the catalyst composition are Pt-Ni, Pd-Ni, Pt-Fe, Pt-Ir or Pt-Co, preferably Pt-Ni.

4. Process according to any of the preceding claims, wherein the at least two different crystalline molecular sieves are selected from USY, ZSM-5 and zeolite beta.

5. Process according to any of the preceding claims, wherein the process is carried out in a tubular bed type reactor having a space velocity in the range of 0.5 to 4.0 h^-1.

6. Process according to any of the preceding claims, wherein the binder comprises gamma-Al₂O₃, SiO₂, ZrO₂, TiO₂ or any mixtures thereof.

7. Process according to any of the preceding claims, wherein the crystalline molecular sieves are in acid form.

8. Catalyst composition for hydrocracking and isomerization of a hydrocarbon feed rich in normal and/or slightly branched paraffins, comprising two different metals from group VIII of the periodic table of elements, the first metal being preferably selected from platinum, palladium or iridium, and the second metal being preferably selected from nickel, cobalt or iron, on a support which comprises at least two different crystalline molecular sieves having each pores with a largest diameter in a range of 0.56-0.74 nm, one of the molecular sieves being preferably ultrastable Y zeolithe (USY), and a binder of up to 25 weight percent, based on the total weight of the support.

Amended claims

Amended claims in accordance with Rule 137(2) EPC.

1. Hydroconversion process which comprises reacting a hydrocarbon feed comprising C₉⁺ normal paraffins and/or mid cut naphtha petroleum fraction with a source of hydrogen in the presence of a catalyst composition which comprises two different metals from group VIII of the periodic table of elements, the first metal being preferably selected from platinum, palladium or iridium, and the second metal being preferably selected from nickel, cobalt or iron, on a support which comprises at least two different crystalline molecular sieves having each pores with a largest diameter in a range of 0.56-0.74 nm, one of the molecular sieves being ultrastable Y zeolite (USY), and a binder of up to 25 weight percent, based on the total weight of the support, at a pressure of about 1-5 bar and at a temperature in the range of 200-300°C, with a hydrogen/feed molar ratio in the range of from 5 to 15 mol/mol.

2. Hydroconversion process according to claim 1, wherein the hydrocarbon feed comprises hydrotreated naphtha.

3. Process according to claim 1 or 2, wherein the two different metals of the catalyst composition are Pt-Ni, Pd-Ni, Pt-Fe, Pt-Ir or Pt-Co, preferably Pt-Ni.

4. Process according to any of the preceding claims, wherein additional crystalline molecular sieves are selected from ZSM-5 and zeolite beta.

5. Process according to any of the preceding claims, wherein the process is carried out in a tubular bed type reactor having a space velocity in the range of 0.5 to 4.0 h^-1.

6. Process according to any of the preceding claims, wherein the binder comprises gamma-Al₂O₃, SiO₂, ZrO₂, TiO₂ or any mixtures thereof.

7. Process according to any of the preceding claims, wherein the crystalline molecular sieves are in acid form.

8. Catalyst composition for hydrocracking and isomerization of a hydrocarbon feed comprising C₉⁺ normal paraffins and/or mid cut naphtha petroleum comprising two different metals from group VIII of the periodic table of elements, the first metal being preferably selected from platinum, palladium or iridium, and the second metal being preferably selected from nickel, cobalt or iron, on a support which comprises at least two different crystalline molecular sieves having each pores with a largest diameter in a range of 0.56-0.74 nm, one of the molecular sieves being ultrastable Y zeolithe (USY), and a binder of up to 25 weight percent, based on the total weight of the support.

Drawing